As is well known in the art, in the manufacture of printed electronic circuits a laminate of copper and etch resistant material, usually plastic, is used. A common method of obtaining the circuits is to mask the desired pattern on the copper surface of the laminate with a protective resist material, which is impervious to the action of an etch solution. In a subsequent etching step, the unprotected areas of the copper are etched away, while the masked areas remain intact and provide the desired circuiting supported by the plastic. The resist material can be a plastic material, an ink or a solder.
In the last few years, the industry has more and more turned to hydrogen peroxide-sulfuric acid systems for etching the electronic circuit boards, due to the low cost of the etching solutions and to the relative ease with which copper values can be recovered from the spent etch solutions.
However, there are many problems connected with the use of hydrogen peroxide as an ingredient in the etchants. It is a well known fact that the stability of hydrogen peroxide in a sulfuric acid-hydrogen peroxide solution is detrimentally affected by the presence of heavy metal ions such as copper ions. Thus, as etching proceeds and copper ion content of the etchant thereby increases, the etch rate will experience a serious drop-off due to the decomposition of the hydrogen peroxide in the etch bath, which will soon be exhausted. In order to improve the capacity of these etchants, various stabilizers have been suggested and used with some success for abatement of the hydrogen peroxide decomposition due to the presence of copper ions.
For instance, lower saturated aliphatic alcohols, such as methanol, ethanol, propanol and butanol, are disclosed in U.S. Pat. No. 3,597,290 as useful stabilizing additives to acidified hydrogen peroxide copper etching solutions. A disadvantage of these stabilized solutions is that they are sensitive to the presence of chloride or bromide ions and therefore precautions must be made to remove these ions from the etching system prior to use, e.g. by deionization or by precipitation of the contaminating ions, e.g. with a silver salt. Also, the alcohols are generally quite volatile at the elevated temperatures required in etching processes, and therefore, substantial losses of the stabilizer are incurred during operation.
Ethylene glycol, either in mono- or poly-form, is another compound which is known to stabilize acidified hydrogen peroxide solutions used in metal dissolution processes such as copper pickling (cf. U.S. Pat. No. 3,537,895) and etching (c.f. U.S. Pat. No. 3,773,577). In addition to the stabilizing effect, ethylene glycol also has other advantages in accordance with the teachings of these patents in that it has a relatively low volatility at normal operating temperatures and that it improves the etching and pickling rates somewhat. However, these rates are still not fast enough for many metal dissolution processes, and the problem of chloride and bromide sensitivity is also present with these stabilized metal treating solutions.
Although considerable retardation of the metal ion-induced hydrogen decomposition can be achieved by the addition of a suitable stabilizer, the etch rates of the stabilized hydrogen peroxide-sulfuric acid etchants have, generally, been quite low and in need of improvement especially at high copper ion concentrations. It has therefore been suggested in the prior art to add a catalyst or promoter to improve the etch rate. Specific examples of such catalysts are the metal ions disclosed in U.S. Pat. No. 3,597,290, such as silver, mercury, palladium, gold and platinum ions, which all have a lower oxidation potential than that of copper. Other examples include those of U.S. Pat. No. 3,293,093, i.e. phenacetin, sulfathiazole and silver ion, or the various combinations of any of the above three components with dibasic acids, as disclosed in U.S. Pat. No. 3,341,384, or with the phenyl ureas or benzoic acids of U.S. Pat. No. 3,407,141, or with the urea and thiourea compounds of U.S. Pat. No. 3,668,131.
Although silver ions thus appear to provide a universal solution to the above-discussed problem of low etch rates as well as that caused by the presence of free chloride and bromide ion content, there are still some disadvantages had with the use of silver ions in preparing hydrogen peroxide-sulfuric acid etch solutions. One of these is the high cost of silver. Another is that silver ions still do not promote the rate of etching as much as would be desired.
An object of the present invention is to provide a novel, highly efficient aqueous composition for the dissolution of metals.
Another object is to provide an improved method for the dissolution of metals, e.g. copper or alloys of copper, at high rates.
Still another object is to provide a composition and method for etching copper, wherein the etch rates are relatively unaffected by the presence of chloride or bromide ions.
Other objects of the invention will become readily apparent from the detailed description set forth hereinafter.